JPH0439446B2 - - Google Patents
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- Publication number
- JPH0439446B2 JPH0439446B2 JP13291183A JP13291183A JPH0439446B2 JP H0439446 B2 JPH0439446 B2 JP H0439446B2 JP 13291183 A JP13291183 A JP 13291183A JP 13291183 A JP13291183 A JP 13291183A JP H0439446 B2 JPH0439446 B2 JP H0439446B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfite
- reaction
- salt
- hydrogen
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 238000006243 chemical reaction Methods 0.000 claims description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- -1 sulfonic acid compound Chemical class 0.000 claims description 8
- 229940079826 hydrogen sulfite Drugs 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 6
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 5
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HVGIUNGSUCQGDX-UHFFFAOYSA-N 3-amino-2-methylpropane-1-sulfonic acid Chemical compound NCC(C)CS(O)(=O)=O HVGIUNGSUCQGDX-UHFFFAOYSA-N 0.000 description 3
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229960003080 taurine Drugs 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- SUPUVLWGKPVHBQ-UHFFFAOYSA-M lithium sulfite Chemical compound [Li+].OS([O-])=O SUPUVLWGKPVHBQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000007059 Strecker synthesis reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FMWMEQINULDRBI-UHFFFAOYSA-L copper;sulfite Chemical compound [Cu+2].[O-]S([O-])=O FMWMEQINULDRBI-UHFFFAOYSA-L 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- WYCFMBAHFPUBDS-UHFFFAOYSA-L silver sulfite Chemical compound [Ag+].[Ag+].[O-]S([O-])=O WYCFMBAHFPUBDS-UHFFFAOYSA-L 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、医薬品あるいは染料用原料として有
用な有機スルホン酸又はその塩の製造方法に関
し、さらに詳しくは、一般式Ｒ−Ｘ（中Ｒは脂肪
族アミン又は芳香族アミンを示し、Ｘはハロゲン
原子を示す。）で表わされる化合物又はハロゲン
化水塩を亜硫酸塩及び／又は亜硫酸水素塩と反応
させて有機スルホン酸化合物又はその塩を製造す
るに当り、過剰量の亜硫酸水素塩の存在下で反応
させることを特徴とする有機スルホン酸又はその
塩の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an organic sulfonic acid or a salt thereof useful as a raw material for pharmaceuticals or dyes. and X represents a halogen atom. The present invention relates to a method for producing an organic sulfonic acid or a salt thereof, which is characterized by carrying out the reaction in the presence of a hydrogen salt.
ハロゲン化有機化合物と亜硫酸塩とを反応させ
る、いわゆるStrecker反応は、スルホン基導入に
極めて有用である。しかし、この方法では、出発
原料のハロゲン化有機化合物と生成した有機スル
ホン酸との間で脱ハロゲン化水素反応が起き、副
反応物が少量又は大量に副生し、精製工程の増
加、副生物の製品への混入、排水処理等の問題を
引き起こし工業的製造には不向きであつた。 The so-called Strecker reaction, in which a halogenated organic compound and a sulfite are reacted, is extremely useful for introducing a sulfone group. However, in this method, a dehydrohalogenation reaction occurs between the halogenated organic compound as the starting material and the organic sulfonic acid produced, resulting in the production of a small amount or large amount of by-products, an increase in the number of purification steps, and the production of by-products. This caused problems such as contamination with products and wastewater treatment, making it unsuitable for industrial production.
本発明者らは、従来法の上記欠点を克服するた
め鋭意研究を重ねた結果、アミノ基を有する、ハ
ロゲン化有機化合物をスルホン化するに当り、反
応系に過剰量の亜硫酸水素塩を存在させることに
より、非有効成分である副反応物の副生が抑制さ
れ、反応生成物の分離、生成が容易になり、安価
に緩和な条件下で有機スルホン酸を製造でき、そ
して排水処理も容易になることを見出し、この知
見に基づき本発明を完成するに至つた。 As a result of intensive research to overcome the above-mentioned drawbacks of conventional methods, the present inventors discovered that when sulfonating a halogenated organic compound having an amino group, an excessive amount of bisulfite is present in the reaction system. This suppresses the production of side reactants, which are inactive ingredients, and facilitates the separation and production of reaction products, making it possible to produce organic sulfonic acids at low cost and under mild conditions, and facilitating wastewater treatment. Based on this finding, we have completed the present invention.
本発明において一般式Ｒ−Ｘで表わされる出発
原料としてのハロゲン化有機化合物を詳しく説明
すれば次の通りである。 A detailed explanation of the halogenated organic compound as a starting material represented by the general formula RX in the present invention is as follows.
式中Ｒは脂肪族アミン又は芳香族アミンを示
す。なおアミノ基は、１つ以上有するものとし、
第一アミン、第二アミン、第三アミンのいずれで
もよい。 In the formula, R represents an aliphatic amine or an aromatic amine. Note that the amino group shall have one or more,
It may be a primary amine, a secondary amine, or a tertiary amine.
Ｒはさらに詳しく例示すると、下記のR′の炭
素原子に結合する１つ又は２つ以上の水素原子が
アミノ基に置換されたものである。 To give a more detailed example of R, one or more hydrogen atoms bonded to the carbon atoms of R' below are substituted with amino groups.
すなわちR′として、アルキルには直鎖状のア
ルキル、分岐状のアルキル、又はアリールが含ま
れる。 That is, as R', alkyl includes linear alkyl, branched alkyl, or aryl.
直鎖状のアルキルとしてはC1〜C18のアルキル
が好ましく、その例としてはメチル、エチル、プ
ロピル、ブチル、ペンチル、ヘキシル、オクチ
ル、ドデシル、オクタデシル、があげられるが、
特に好ましいものはC1〜C8のアルキルである。
分岐状のアルキルとしてはC3〜C18のアルキルが
好ましく、その例としては、イソブチル、２−メ
チルブチル、２−メチルヘプチル、イソヘキシ
ル、ネオペンチル、イソペンチル、３−メチルヘ
プチル、イソプロピル、sec−ブチル、１−メチ
ルペンチル、tert−ブチル、tert−ペンチルがあ
げられるが、特に好ましいものはC3〜C8のもの
である。またアリール、としては、フエニル、ナ
フチル等があげられる。なおR′が上記例示のも
のに限定されないことはもちろんである。 The straight chain alkyl is preferably a C1 to C18 alkyl, examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, and octadecyl.
Particularly preferred is C1 - C8 alkyl.
The branched alkyl is preferably a C3 to C18 alkyl, such as isobutyl, 2-methylbutyl, 2-methylheptyl, isohexyl, neopentyl, isopentyl, 3-methylheptyl, isopropyl, sec-butyl, 1 Examples include -methylpentyl, tert-butyl, and tert-pentyl, and particularly preferred are C3 to C8 . Examples of aryl include phenyl and naphthyl. It goes without saying that R' is not limited to those exemplified above.
次に、式中Ｘは、ハロゲン原子であるが塩素原
子又は臭素原子が好ましい。 Next, in the formula, X is a halogen atom, preferably a chlorine atom or a bromine atom.
また、一般式Ｒ−Ｘで示される化合物のハロゲ
ン化水素塩は、通常上記Ｘに対応するハロゲン化
水素の塩である。 Further, the hydrogen halide salt of the compound represented by the general formula R-X is usually a salt of hydrogen halide corresponding to the above-mentioned X.
次に亜硫酸塩としては亜硫酸リチウム、亜硫酸
ナトリウム、亜硫酸カリウム、亜硫酸銀、亜硫酸
銅、亜硫酸カルシウム、亜硫酸アンモニウムなど
が挙げられる。また亜硫酸水素塩としては亜硫酸
水素リチウム、亜硫酸水素ナトリウム、亜硫酸水
素カリウム、亜硫酸水素アンモニウムなどが挙げ
げられる。ただし、亜硫酸塩及び亜硫酸水素塩は
上記例示の塩に限定されるものでなく、その他の
塩を用いてもよい。 Examples of sulfites include lithium sulfite, sodium sulfite, potassium sulfite, silver sulfite, copper sulfite, calcium sulfite, and ammonium sulfite. Further, examples of the bisulfite include lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, and ammonium hydrogen sulfite. However, the sulfite and hydrogen sulfite are not limited to the salts exemplified above, and other salts may be used.
本発明の方法は無溶媒であるいは溶媒を用いて
行う。溶媒としては水、アルコール類、ケトン
類、環状エーテル類等が挙げられるが、特に好ま
しいのは水、又は水と他の溶媒との混合物であ
る。 The method of the present invention is carried out without a solvent or with a solvent. Examples of the solvent include water, alcohols, ketones, cyclic ethers, etc., and particularly preferred is water or a mixture of water and other solvents.
反応時間は10分ないし50時間で十分である。反
応圧力は通常、常圧で十分であるが、オートクレ
ーブを用い加圧下で行つてもよい。反応温度は20
℃ないし300℃の範囲である。 A reaction time of 10 minutes to 50 hours is sufficient. Normal pressure is usually sufficient for the reaction pressure, but the reaction may also be carried out under increased pressure using an autoclave. The reaction temperature is 20
It ranges from ℃ to 300℃.
反応系に亜硫酸塩あるいは亜硫酸水素塩ととも
に過剰量存在させる亜硫酸水素塩の量は一般式Ｒ
−Ｘで表わされるハロゲン化有機化合物に対し
1.01〜10倍モル過剰とするのがよいが、好ましく
は２〜５倍モル過剰に用いるのがよい。この場合
亜硫酸水素塩の量が少ないと副反応物の生成を完
全に抑制することができない。また、多すぎると
その分離回収が繁雑になり経済的ではない。 The amount of hydrogen sulfite present in excess along with sulfite or hydrogen sulfite in the reaction system is expressed by the general formula R
For halogenated organic compounds represented by -X
It is preferable to use a 1.01- to 10-fold molar excess, preferably a 2- to 5-fold molar excess. In this case, if the amount of bisulfite is small, the formation of side reactants cannot be completely suppressed. In addition, if the amount is too large, separation and recovery becomes complicated and uneconomical.
本発明方法によれば、副生物の生成が著しく抑
制されると共に、緩和な条件下で高収率で目的の
有機スルホン酸を得ることができる。したがつ
て、有機スルホン酸の分離、精製が容易であり、
排水処理に対する負荷も著しく軽減される。 According to the method of the present invention, the production of by-products is significantly suppressed, and the desired organic sulfonic acid can be obtained in high yield under mild conditions. Therefore, it is easy to separate and purify the organic sulfonic acid,
The burden on wastewater treatment is also significantly reduced.
次に本発明を実施例に基づきさらに詳細に説明
する。 Next, the present invention will be explained in more detail based on examples.
実施例 １
撹拌器、温度計、滴下漏斗及び冷却管を備えた
四つ口フラスコ中に亜硫酸ナトリウム0.4モルと
亜硫酸水素ナトリウム2.0モルをとり、水350mlに
溶解させ、100℃に昇温させたのちｐ−クロルア
ニリン0.4モルの水溶液で５時間で滴下し、滴下
終了後さらに５時間100℃に保持して熟成を行つ
た。この合成により、４−アミノベンゼンスルホ
ン酸ナトリウムが転化率78％で得られた。残りは
未反応ｐ−クロルアニリンであつた。Example 1 0.4 mol of sodium sulfite and 2.0 mol of sodium bisulfite were placed in a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and cooling tube, dissolved in 350 ml of water, and heated to 100°C. An aqueous solution of 0.4 mol of p-chloroaniline was added dropwise over a period of 5 hours, and after the addition was completed, the mixture was maintained at 100° C. for an additional 5 hours for ripening. This synthesis yielded sodium 4-aminobenzenesulfonate at a conversion rate of 78%. The remainder was unreacted p-chloroaniline.
比較例 １
実施例１と同様の反応装置を使用し、亜硫酸水
素ナトリウムを使用しなかつた以外は実施例１と
全く同様にして反応を行つたところ、４−アミノ
ベンゼンスルホン酸ナトリウムが転化率58％で得
られた。このとき４−アミノベンゼンスルホン酸
ナトリウムとｐ−クロルアニリンとの反応及びそ
の重合物が15％副生していた。残りは未反応ｐ−
クロルアニリンであつた。Comparative Example 1 A reaction was carried out in exactly the same manner as in Example 1, except that the same reaction apparatus as in Example 1 was used, and sodium hydrogen sulfite was not used. Obtained in %. At this time, 15% of the reaction between sodium 4-aminobenzenesulfonate and p-chloroaniline and its polymer was produced as a by-product. The rest is unreacted p-
It was chloraniline.
実施例 ２
実施例１と同様な反応装置を用い、亜硫酸ナト
リウム0.4モルと亜硫酸水素ナトリウム1.2モルを
水200に溶解させ、80℃に昇温させたのち、0.4モ
ルのクロルエチルアミン塩酸塩水溶液を３時間か
けて滴下し、滴下終了後さらに４時間80℃に保持
して熟成を行つた。この合成により、２−アミノ
エタンスルホン酸が転化率92％で得られた。残り
は未反応クロルエチルアミン及びクロルエチルア
ミンの原料となるモノエタノールアミン塩酸塩で
あつた。Example 2 Using a reaction apparatus similar to Example 1, 0.4 mol of sodium sulfite and 1.2 mol of sodium bisulfite were dissolved in 200°C of water, heated to 80°C, and then 0.4 mol of an aqueous solution of chloroethylamine hydrochloride was dissolved in 3 mol of water. The solution was added dropwise over a period of time, and after completion of the addition, the solution was maintained at 80° C. for an additional 4 hours for ripening. Through this synthesis, 2-aminoethanesulfonic acid was obtained with a conversion rate of 92%. The remainder was unreacted chloroethylamine and monoethanolamine hydrochloride, which is a raw material for chlorethylamine.
比較例 ２
亜硫酸水素ナトリウムを使用しなかつた以外は
実施例２と全く同様にして実施例２と同様の装置
を用いて反応を行わせたところ、２−アミノエタ
ンスルホン酸が転化率85％で得られた。このと
き、２−アミノエタンスルホン酸とクロルエチル
アミンとの反応物及びその重合物が12％副生して
いた。残りは未反応クロルエチルアミンとモノエ
タノールアミン塩酸塩であつた。Comparative Example 2 A reaction was carried out in exactly the same manner as in Example 2, except that sodium hydrogen sulfite was not used, using the same apparatus as in Example 2, and 2-aminoethanesulfonic acid was produced at a conversion rate of 85% Obtained. At this time, 12% of the reaction product of 2-aminoethanesulfonic acid and chloroethylamine and its polymer were produced as by-products. The remainder was unreacted chloroethylamine and monoethanolamine hydrochloride.
実施例 ３
実施例１と同様な反応装置を用い、亜硫酸ナト
リウム0.4モルと亜硫酸水素ナトリウム1.8モルを
水300mlに溶解し、80℃に昇湿させたのち、0.4モ
ルの３−クロル−２−メチルプロピルアミン塩酸
塩水溶液を３時間で滴下し、滴下終了後さらに５
時間80℃で熟成させた。この合成により、３−ア
ミノ−２−メチルプロパンスルホン酸が転化率88
％で得られた。残りは未反応３−クロル−２−メ
チルプロピルアミン及び３−クロル−２−メチル
プロピルアミンの原料となる２−メチル−３−プ
ロパノールアミン塩酸塩であつた。Example 3 Using the same reaction apparatus as in Example 1, 0.4 mol of sodium sulfite and 1.8 mol of sodium hydrogen sulfite were dissolved in 300 ml of water, the temperature was raised to 80°C, and 0.4 mol of 3-chloro-2-methyl was dissolved. Propylamine hydrochloride aqueous solution was added dropwise over 3 hours, and after the addition was completed, an additional 5
It was aged at 80°C for an hour. This synthesis produced 3-amino-2-methylpropanesulfonic acid with a conversion rate of 88
Obtained in %. The remainder was unreacted 3-chloro-2-methylpropylamine and 2-methyl-3-propanolamine hydrochloride, which is a raw material for 3-chloro-2-methylpropylamine.
比較例 ３
亜硫酸水素ナトリウムを使用しなかつた以外は
実施例２と全く同様にして実施例３と同様の装置
を用いて反応を行わせたところ、３−アミノ−２
−メチルプロパンスルホン酸が転化率81％で得ら
れた。このとき、３−アミノ−２−メチルプロパ
ンスルホン酸と、３−クロル−２−メチルプロピ
ルアミンとの反応物及びその重合物が15％副生し
ていた。残りは未反応３−クロル−２−メチルプ
ロピルアミンと、２−メチル−３−プロパノール
アミン塩酸塩であつた。Comparative Example 3 A reaction was carried out in exactly the same manner as in Example 2 except that sodium hydrogen sulfite was not used, using the same apparatus as in Example 3. As a result, 3-amino-2
-Methylpropanesulfonic acid was obtained with a conversion rate of 81%. At this time, 15% of the reaction product of 3-amino-2-methylpropanesulfonic acid and 3-chloro-2-methylpropylamine and its polymer were produced as by-products. The remainder was unreacted 3-chloro-2-methylpropylamine and 2-methyl-3-propanolamine hydrochloride.
Claims (1)
香族アミンを示し、Ｘはハロゲン原子を示す。）
で表わされる化合物又はそのハロゲン化水素塩を
亜硫酸塩及び／又は亜硫酸水素塩と反応させて有
機スルホン酸化合物又はその塩を製造するに当
り、過剰量の亜硫酸水素塩の存在下で反応させる
ことを特徴とする有機スルホン酸又はその塩の製
造方法。1 General formula R-X (wherein R represents an aliphatic amine or aromatic amine, and X represents a halogen atom)
When producing an organic sulfonic acid compound or its salt by reacting the compound represented by or its hydrogen halide salt with a sulfite and/or hydrogen sulfite, the reaction must be carried out in the presence of an excess amount of hydrogen sulfite. A method for producing a characterized organic sulfonic acid or its salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13291183A JPS6025937A (en) | 1983-07-22 | 1983-07-22 | Production of organic sulfonic acid or its salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13291183A JPS6025937A (en) | 1983-07-22 | 1983-07-22 | Production of organic sulfonic acid or its salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6025937A JPS6025937A (en) | 1985-02-08 |
| JPH0439446B2 true JPH0439446B2 (en) | 1992-06-29 |
Family
ID=15092404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13291183A Granted JPS6025937A (en) | 1983-07-22 | 1983-07-22 | Production of organic sulfonic acid or its salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025937A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0519243A2 (en) * | 2004-12-22 | 2009-01-06 | Neurochem Int Ltd | Methods and compositions for treating amyloid-related diseases |
| DK2089417T3 (en) | 2006-10-12 | 2015-03-23 | Bhi Ltd Partnership | Methods, Compounds, Compositions and Vehicles for Delivery of 3-Amion-1-Propanesulfonic Acid |
-
1983
- 1983-07-22 JP JP13291183A patent/JPS6025937A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6025937A (en) | 1985-02-08 |
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